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WO2013069365A1 - Composition de résine thermoplastique et corps moulé formé à partir de celle-ci - Google Patents

Composition de résine thermoplastique et corps moulé formé à partir de celle-ci Download PDF

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Publication number
WO2013069365A1
WO2013069365A1 PCT/JP2012/072680 JP2012072680W WO2013069365A1 WO 2013069365 A1 WO2013069365 A1 WO 2013069365A1 JP 2012072680 W JP2012072680 W JP 2012072680W WO 2013069365 A1 WO2013069365 A1 WO 2013069365A1
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Prior art keywords
thermoplastic resin
resin composition
acid
filler
rosin
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PCT/JP2012/072680
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English (en)
Japanese (ja)
Inventor
夕哉 正鋳
顕 伊藤
将 甲斐原
幹夫 古川
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Unitika Ltd
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Unitika Ltd
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Priority to CN201280045883.7A priority Critical patent/CN103814082B/zh
Priority to JP2013542887A priority patent/JP6061863B2/ja
Publication of WO2013069365A1 publication Critical patent/WO2013069365A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin

Definitions

  • the present invention relates to a thermoplastic resin composition excellent in mechanical properties and molding processability, and a molded body comprising the same.
  • a resin composition in which a reinforcing filler such as talc or glass fiber is blended with a resin is used for manufacturing a resin molded body.
  • a resin composition containing the reinforcing filler By molding the resin composition containing the reinforcing filler, a molded body with improved strength can be obtained.
  • the resin composition containing the reinforcing filler has low fluidity and poor molding processability, it has been particularly difficult to form a thin molded article having a complicated shape.
  • LED devices have been developed, and the light emission efficiency has been greatly improved.
  • the demand for LED devices in lighting applications has increased rapidly.
  • a part of the electric energy is converted into heat energy at that portion, and heat is generated.
  • the LED element itself becomes a resistance, and heat is generated simultaneously with light emission. Since the LED element is vulnerable to heat, it is known that when the temperature exceeds a prescribed temperature, the light emission efficiency is lowered and the life of the LED element is affected. For this reason, in an apparatus using an LED device, the temperature of the LED element must be kept below a standard value.
  • Patent Literature 1 proposes an LED lighting device in which a metal heat dissipating fin is provided in the housing portion.
  • a metal heat dissipating fin is provided in the housing portion.
  • such a metal casing has a problem that the LED lighting device itself becomes heavy and the processing cost becomes high. Based on such a background, in order to reduce the weight of the equipment and improve the design flexibility of the member, it is desired to form the casing by injection molding using a resin having excellent heat conduction. .
  • a resin has a lower thermal conductivity than a metal or the like, and sufficient heat dissipation cannot be obtained as it is.
  • a method for improving the heat dissipation of the resin a method of blending a filler having excellent thermal conductivity is generally used, and a large amount of a highly thermally conductive filler is blended in order to develop high thermal conductivity.
  • a resin composition containing a large amount of a high thermal conductive filler has a high melt viscosity at the time of melting, so that the workability at the time of injection molding is greatly reduced.
  • the resin composition in which fillers such as the reinforcing filler and the high thermal conductive filler are blended as described above, as a method for improving flowability and improving molding processability, the resin composition may be aliphatic. It is known to add hydrocarbons, polyolefin waxes, higher fatty acids, aliphatic alcohols, fatty acid amides, metal soaps, fatty acid esters and the like as lubricants, and to add conventionally known plasticizers. Patent Document 2 discloses that a rosin acid derivative such as rosinamide or rosin acid ester is added as a resin processability improver.
  • An object of the present invention is to provide a thermoplastic resin composition with improved molding processability and a molded article having excellent mechanical properties and no bleed-out.
  • the present inventors have added a rosin having an acid value of 60 mgKOH / g or more to a resin composition containing a thermoplastic resin and a filler.
  • the present inventors have found that the above problems can be solved and have reached the present invention.
  • thermoplastic resin composition containing a thermoplastic resin (A), a filler (B) and a rosin (C), wherein the thermoplastic resin (A) is a polyamide resin (A1), an aliphatic polyester resin ( A2) or a semi-aromatic polyester resin (A3), and the content of rosin (C) is 0.3 to 5 parts by mass with respect to 100 parts by mass in total of the thermoplastic resin (A) and the filler (B), A thermoplastic resin composition, wherein the acid value of rosin (C) is 60 mgKOH / g or more.
  • thermoplastic resin composition according to (1) wherein the volume ratio (A / B) between the thermoplastic resin (A) and the filler (B) is 90/10 to 20/80. .
  • the thermoplastic resin composition as described in (1) or (2), wherein the semi-aromatic polyester resin (A3) is polybutylene terephthalate or polyethylene terephthalate.
  • the filler (B) is a flaky graphite having an average particle diameter of 30 ⁇ m or more, a flaky boron nitride having a hexagonal crystal structure and having an average particle diameter of 15 ⁇ m or more, talc having an average particle diameter of 15 ⁇ m or more, and an average particle diameter of 30 ⁇ m.
  • the molded body according to (8), wherein the molded body is a housing for an LED lighting device.
  • thermoplastic resin composition excellent in moldability can be provided, and a molded article having excellent mechanical properties and no bleed-out can be provided. Further, the resin composition of the present invention has excellent moldability even when a large amount of filler is contained or a filler having a large particle size is used.
  • a material having thermal conductivity as the filler By using, for example, a material having thermal conductivity as the filler, a molded body having excellent heat dissipation can be obtained, and this molded body is suitably used for a housing of an electronic device such as an LED lighting device. be able to.
  • FIG. 1 is a structural example of an LED bulb using the housing for an LED lighting device of the present invention.
  • FIG. 2 shows an evaluation model used for the heat dissipation evaluation of the example.
  • thermoplastic resin composition of the present invention contains a thermoplastic resin (A), a filler (B), and rosin (C).
  • thermoplastic resin (A) a polyamide resin (A1), an aliphatic polyester resin (A2), or a semi-aromatic polyester resin (A3) is used as the thermoplastic resin (A).
  • the polyamide resin (A1) used in the present invention is a homopolyamide or copolyamide having an amide bond, or a mixture thereof.
  • a homopolyamide or copolyamide having an amide bond can be obtained by polymerizing lactam, aminocarboxylic acid, diamine, or dicarboxylic acid.
  • polyamide resin (A1) examples include polycapramide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polycoupleramide / polyhexamethylene adipamide copolymer (nylon) 6/66), polyundecamide (nylon 11), polycapramide / polyundecamide copolymer (nylon 6/11), polydodecamide (nylon 12), polycoupler / polydodecanamide copolymer (nylon 6/12), polyhexamethylene sebacamide (Nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalamide ( Iron 6T), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polycapramide /
  • Examples of the aliphatic polyester (A2) used in the present invention include polycondensates from aliphatic dicarboxylic acids and aliphatic diols, polycondensates of aliphatic hydroxycarboxylic acids, and the like. Etc. are not particularly limited.
  • aliphatic polyester (A2) examples include polybutylene sebacate, polybutylene succinate, polybutylene succinate / adipate, polypropylene sebacate, polypropylene succinate, polypropylene succinate / adipate, polylactic acid, polyglycolic acid and the like Among these, polylactic acid is preferred from the viewpoints of the environmental aspect that the raw material is derived from plants, heat resistance, and moldability.
  • polylactic acid used in the present invention examples include poly (L-lactic acid), poly (D-lactic acid), a mixture of poly (L-lactic acid) and poly (D-lactic acid), poly (L-lactic acid) and poly (L-lactic acid). D-lactic acid), stereocomplexes, and the like.
  • polylactic acid mainly composed of poly (L-lactic acid) is preferably used from the viewpoint of heat resistance and moldability.
  • Polylactic acid is preferably derived from plants such as corn, and more preferably from non-edible plants, since it can reduce environmental burden.
  • the melting point of polylactic acid mainly composed of poly (L-lactic acid) varies depending on the optical purity, but in the present invention, the mechanical strength, impact resistance and heat resistance of the molded product obtained by molding the resin composition are improved. In consideration, it is preferably 160 ° C. or higher. In order to set the melting point to 160 ° C. or higher, the ratio of poly (D-lactic acid) may be less than about 3 mol%.
  • the weight average molecular weight of polylactic acid is preferably 50,000 to 300,000, more preferably 100,000 to 300,000, and further preferably 120,000 to 200,000. When the weight average molecular weight is less than 50,000, it is difficult to obtain practical strength and durability. On the other hand, when the weight average molecular weight exceeds 300,000, the fluidity is low, and melt extrusion tends to be difficult.
  • the weight average molecular weight of polylactic acid is calculated by a method of analyzing by gel permeation chromatography (GPC).
  • Polylactic acid is produced by a known melt polymerization method or by further adding a solid phase polymerization method.
  • a cross-linked or branched structure may be introduced into the polylactic acid.
  • the heat resistance of polylactic acid can be improved.
  • methods for introducing a crosslinked structure include a method of adding a peroxide, a method of using a peroxide and a radical polymerizable compound in combination, a method of irradiating radiation, a method of using a polyfunctional compound as a crosslinking agent, and the like.
  • the peroxide used for introducing a crosslinked structure include dibutyl peroxide and bis (butylperoxy) diisopropylbenzene.
  • radical polymerizable compound examples include glycidyl dimethacrylate, ethylene glycol dimethacrylate, and polyethylene glycol diester.
  • polyfunctional compound examples include ethylene-vinyl alcohol copolymer, partially saponified polyvinyl alcohol, and cellulose diacetate.
  • the method for introducing a branched structure examples include a method in which a tri- or higher functional monomer is copolymerized with L-lactic acid or D-lactic acid, and a method in which a macromonomer is graft-polymerized to polylactic acid.
  • Examples of the tri- or higher functional monomer used for introducing a branched structure include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, malic acid, glyceric acid, citric acid, tartaric acid, and the like.
  • the compound is not particularly limited as long as it is a compound capable of binding to the asymmetric carbon present in the lactic acid resin, and examples thereof include ⁇ -olefins such as 1-hexene.
  • the semi-aromatic polyester (A3) used in the present invention is a semi-aromatic polyester obtained by polycondensation of a dicarboxylic acid compound and a dihydroxy compound, polycondensation of an oxycarboxylic acid compound or polycondensation of a mixture of these three components. Even if it is any of homopolyester and copolyester, the effect of this invention can be show
  • the semi-aromatic polyester (A3) include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polycyclohexylenedimethylene terephthalate.
  • polybutylene terephthalate and polyethylene terephthalate are preferable in terms of moldability and economy.
  • the polybutylene terephthalate used in the present invention is a polymer obtained by a polycondensation reaction between terephthalic acid or its ester-forming derivative and 1,4-butanediol or its ester-forming derivative.
  • Polybutylene terephthalate may be copolymerized with terephthalic acid or an ester-forming derivative thereof together with isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, dodecanedioic acid, oxalic acid or an ester-forming derivative thereof.
  • 1,4-butanediol or ester-forming derivatives thereof ethylene glycol, propylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, molecular weight 400 ⁇ 6000 polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol or ester-forming derivatives thereof may be copolymerized.
  • the polyethylene terephthalate used in the present invention is mainly composed of terephthalic acid and ethylene glycol.
  • Polyethylene terephthalate is used as an acid component other than terephthalic acid, for example, aromatic dicarboxylic acids such as isophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and diphenylsulfonedicarboxylic acid.
  • aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid and their anhydrides
  • copolymerized with aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid May be.
  • Polyethylene terephthalate is an alcohol component other than ethylene glycol, for example, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4 -Aliphatic diols such as butanediol, 2,3-butanediol, diethylene glycol, 1,5-pentanediol, neopentyl glycol, triethylene glycol, polyethylene glycol; aliphatic polyhydric alcohols such as trimethylolpropane, pentaerythritol; Alicyclic diols such as 1,4-cyclohexanedimethanol and 1,4-cyclohexanediethanol; aromatic diols such as ethylene oxide adducts of bisphenol A and bisphenol S; 4-hydroxybenzoic acid; Hydroxycarboxylic acid may be copolymerized in such Rorakuton
  • the copolymer component is preferably used within a range that does not impair the properties of polyethylene terephthalate, and is preferably less than 5 mol% with respect to 100 mol% each of the acid component and alcohol component constituting polyethylene terephthalate. If it exceeds 5 mol%, the mechanical properties may be impaired or the fluidity may be lowered.
  • the resin composition of the present invention contains a filler (B).
  • the filler (B) is not particularly limited, but is used for the purpose of improving mechanical properties, thermal properties, etc., conductivity, thermal conductivity, magnetism, piezoelectricity, electromagnetic wave absorption, flame retardancy, What is used in order to provide ultraviolet absorption etc. can be utilized.
  • the resin composition may contain two or more fillers (B).
  • the volume ratio (A / B) between the thermoplastic resin (A) and the filler (B) is preferably 90/10 to 20/80, more preferably 80/20 to 30 / 70 is more preferable, and 65/35 to 35/65 is even more preferable.
  • Examples of the form of the filler (B) include a spherical shape, a powder shape, a fiber shape, a needle shape, a scale shape, a scale shape, a whisker shape, a microcoil shape, and a nanotube shape.
  • Examples of the filler (B) include acetylene black, ketjen black, carbon nanotube, carbon nanofiber, metal powder (silver, copper, aluminum, titanium, nickel, tin, iron, stainless steel, etc.), conductive zinc oxide, Tin oxide, indium oxide, various ferrites, magnetic iron oxide, aluminum oxide, magnesium oxide, zinc oxide, magnesium carbonate, silicon carbide, aluminum nitride, boron nitride, silicon nitride, carbon, graphite, barium titanate, lead zirconate titanate , Potassium titanate, zonotrite, mica, talc, montmorillonite, hydrotalcite, calcium carbonate, zinc carbonate, wollastonite, barium sulfate, molybdenum disulfide, Teflon (registered trademark) powder, silica, glass beads, glass balloon, oxidation titanium Aluminum hydroxide, magnesium hydroxide, antimony trioxide, boric acid, zinc borate, cerium oxide, calcium oxide,
  • thermal conductivity can be imparted to the resin composition.
  • the thermally conductive filler may be either conductive or insulating, but preferably has a thermal conductivity of 5 W / m ⁇ K or more.
  • the thermal conductivity of the thermally conductive filler can be measured using the sintered product.
  • thermally conductive fillers representative values of thermal conductivity in parentheses (unit: W / (m ⁇ K) are shown in parentheses), talc (5 to 10), aluminum oxide (36) , Magnesium oxide (60), zinc oxide (25), magnesium carbonate (15), silicon carbide (160), aluminum nitride (170), boron nitride (210), silicon nitride (40), carbon (10 to several hundred) Inorganic fillers such as graphite (10 to several hundred), silver (427), copper (398), aluminum (237), titanium (22), nickel (90), tin (68), iron (84), Examples thereof include metallic fillers such as stainless steel (15). These may be used alone or in combination of two or more.
  • graphite and boron nitride are preferably used because of their high thermal conductivity when blended with the thermoplastic resin (A). Moreover, it is preferable to use a talc, magnesium oxide, and aluminum oxide from the point of economical efficiency.
  • Examples of the form of graphite include a spherical shape, a powder shape, a fiber shape, a needle shape, a scale shape, a whisker shape, a microcoil shape, and a nanotube shape.
  • scaly graphite is more preferable because it can increase the heat conduction efficiency when blended with the thermoplastic resin (A).
  • the scale-like graphite has higher thermal conductivity as the average particle size is larger.
  • the mechanical properties tend to decrease, and the mechanical properties and thermal conductivity are uniform without causing agglomeration due to poor dispersion.
  • the average particle size of the scaly graphite is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 30 ⁇ m or more, A thickness of 30 to 200 ⁇ m is particularly preferable.
  • talc examples include a plate shape, a scale shape, a scale shape, and a flake shape.
  • scaly talc and lamellar talc are more preferable because they are easily oriented in the surface direction when formed into a molded body, and as a result, the thermal conductivity can be increased.
  • the average particle size of the scaly talc is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, further preferably 15 ⁇ m or more, and particularly preferably 15 to 70 ⁇ m. preferable.
  • boron nitride examples include a plate shape, a scale shape, and a flake shape. Among these, scaly boron nitride is more preferable because it is easily oriented in the surface direction when formed into a molded body, and as a result, the thermal conductivity can be increased.
  • the average particle size of the flaky boron nitride is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, further preferably 15 ⁇ m or more, and preferably 15 to 70 ⁇ m. Particularly preferred.
  • the crystal system of boron nitride is not particularly limited, and boron nitride having any crystal structure such as hexagonal system, cubic system, and the like is applicable. Of these, boron nitride having a hexagonal crystal structure is preferable because of its high thermal conductivity.
  • Examples of the form of magnesium oxide include a spherical shape, a fiber shape, a spindle shape, a rod shape, a needle shape, a cylindrical shape, and a column shape.
  • spherical magnesium oxide is more preferable because it can improve the moldability.
  • the average particle diameter of the spherical magnesium oxide is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, further preferably 30 ⁇ m or more, and particularly preferably 30 to 80 ⁇ m. preferable.
  • Examples of the form of aluminum oxide include a spherical shape, a fiber shape, a spindle shape, a rod shape, a needle shape, a cylindrical shape, and a column shape.
  • spherical aluminum oxide is more preferable because it can improve the moldability.
  • the average particle diameter of the spherical aluminum oxide is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, further preferably 30 ⁇ m or more, and particularly preferably 30 to 80 ⁇ m. preferable.
  • the filler (B) used in the present invention may be subjected to a surface treatment with a silane coupling agent or a titanium coupling agent in order to improve adhesion with the thermoplastic resin (A).
  • silane coupling agents include ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyldimethoxymethylsilane, etc.
  • Aminosilane coupling agents Epoxysilane coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.
  • the titanium coupling agent include isopropyl tristearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, and tetraisopropyl bis (dioctyl phosphite) titanate. These may be used alone or in combination of two or more.
  • the resin composition of the present invention needs to contain rosin (C).
  • rosin (C) By containing rosin (C), the resin composition can improve the molding processability. In particular, even when a large amount of filler is contained, a filler having a large particle size is used. Even if it is a case, it can have the outstanding moldability, and the molded object obtained can maintain a mechanical characteristic, and does not bleed out.
  • the rosin (C) in the present invention is a diterpenic acid compound called resin acid (rosin acid).
  • resin acid resin acid
  • examples of rosin (C) include natural rosin, modified rosin, and polymerized rosin.
  • Natural rosin is a mixture of resin acids collected from Pinaceae plants.
  • the main component of the resin acid is abietic acid, and further includes neoabietic acid, dehydroabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, levopimaric acid, and the like.
  • Modified rosin is a modified natural rosin such as hydrogenated rosin such as dihydroabietic acid and tetrahydroabietic acid, disproportionated rosin such as dehydroabietic acid and dihydroabietic acid, acrylic acid, maleic acid and fumaric acid.
  • Examples thereof include acid-modified rosin obtained by modifying natural rosin with an acid or the like, and esters thereof.
  • the polymerized rosin is a product obtained by reacting natural rosins or modified rosins, and examples thereof include dimerized products and trimerized products.
  • the acid value of rosin (C) needs to be 60 mgKOH / g or more, preferably 100 mgKOH / g or more, more preferably 180 mgKOH / g or more, and 200 mgKOH / g or more. More preferably.
  • the acid value of rosin (C) is less than 60 mgKOH / g, molding processability may not be improved.
  • the content of rosin (C) must be 0.3 to 5 parts by mass with respect to a total of 100 parts by mass of the thermoplastic resin (A) and the filler (B), and 0.5 to It is preferably 3 parts by mass.
  • the content of rosin (C) is less than 0.3 parts by mass, molding processability may not be improved.
  • the content of rosin (C) exceeds 5 parts by mass, the resulting molded body machine The mechanical characteristics may be significantly reduced and the heat resistance may be significantly reduced.
  • the softening temperature of rosin (C) is preferably 110 ° C. or higher, and more preferably 120 ° C. or higher.
  • rosin (C) having a softening temperature of 110 ° C. or higher decomposition of rosin (C) itself during molding can be suppressed, and rosin (C) can be prevented from bleeding out from the molded body.
  • the heat resistance fall of a molded object can also be suppressed.
  • the resin composition of the present invention includes a heat stabilizer, an antioxidant, a flame retardant, a crystal nucleating agent, a compatibilizing agent, a pigment, a weathering agent, a lubricant, a release agent, and an antistatic agent.
  • An agent or the like may be added.
  • heat stabilizers and antioxidants include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, and halides such as alkali metals.
  • Examples of the flame retardant include inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, and antimony trioxide exemplified as the filler (B), nitrogen-containing compounds such as melamine and guanidine, phosphorus flame retardants, and halogen-based flame retardants. Examples include flame retardants.
  • Examples of the crystal nucleating agent include sorbitol compounds, benzoic acid, metal salts of the compounds, and phosphate ester metal salts.
  • Examples of the compatibilizer include ionomer compatibilizers, oxazoline compatibilizers, elastomer compatibilizers, reactive compatibilizers, and copolymer-based compatibilizers.
  • As the pigment both organic and inorganic pigments can be used.
  • the casing for the LED lighting device is often preferred to be white, and a white pigment is added to the resin composition for molding the case.
  • the white pigment include titanium oxide, zinc oxide, barium sulfate, calcium carbonate, aluminum oxide and the like exemplified as the filler (B), zinc sulfide, zinc sulfate and the like. Among them, reflectance, concealability, etc. Titanium oxide is preferable because the optical properties of the film are improved. Titanium oxide is preferably a rutile type having a high refractive index and good light stability, and the particle diameter is preferably 0.05 to 2.0 ⁇ m, more preferably 0.05 to 0.5 ⁇ m. .
  • Titanium oxide may be surface-treated with a metal oxide such as alumina, silica, zinc oxide and zirconium oxide, an organic acid such as stearic acid, and a surface treatment agent such as a silane coupling agent and a titanium coupling agent. These additives may be used alone or in combination of two or more. In addition, the method of mixing these in this invention is not specifically limited.
  • the resin composition of the present invention comprises a thermoplastic resin (A), a filler (B), and rosin (C), and further various additives as necessary, a general extruder, for example, uniaxial It can manufacture by melt-kneading using an extruder, a twin screw extruder, a roll kneader, and a Brabender. At this time, it is effective to use a static mixer or a dynamic mixer together. In order to improve the kneading state, it is preferable to use a twin screw extruder. Although it does not specifically limit as an addition method of a filler (B), In the extruder, the method of adding from a hopper or using a side feeder is mentioned.
  • the resin composition of the present invention can be molded into a desired shape using a generally known melt molding method such as injection molding, compression molding, extrusion molding, transfer molding, sheet molding, or the like to obtain a molded body. It is preferable to shape
  • the resin composition heated and melted in the cylinder of the injection molding machine is weighed for each shot, injected into the mold in a molten state, cooled and solidified in a predetermined shape, and then taken out from the mold as a molded body. It is.
  • the resin temperature at the time of injection molding needs to be not less than the melting point of the resin composition, and is preferably less than (melting point + 100 ° C.).
  • the resin composition of the present invention is a sealing material for semiconductor elements, resistors, etc., including portable electronic device casings and LED lighting device casings; connectors, sockets, relay parts, coil bobbins, optical pickups, oscillators, and computers.
  • Electrical / electronic parts such as parts; household electrical product parts such as VTR, TV, iron, air conditioner, stereo, vacuum cleaner, refrigerator, rice cooker, lighting equipment; heat from electronic parts such as heat-dissipating sheets, heat sinks, and fans Heat-dissipating member for escaping the lamp; lighting fixture parts such as lamp socket, lamp reflector, lamp housing; acoustic product parts such as compact disc, laser disc (registered trademark), speaker; ferrule for optical cable, mobile phone, fixed phone, facsimile, modem Communication equipment parts such as: Copying machines such as separation nails and heater holders, printing machines Linkage parts; machine parts such as impellers, fan gears, gears, bearings, motor parts and cases; automotive parts such as automotive mechanical parts, engine parts, parts in the engine room, electrical parts, interior parts; microwave cooking pans, It can be applied to molding cooking utensils such as heat-resistant tableware; aircraft, spacecraft, space equipment parts; sensor parts.
  • melt viscosity About the pellet of the resin composition, the melt viscosity at the temperature described in a table
  • Deflection temperature under load (DTUL) Using the test piece prepared in (6) above, the deflection temperature under load of 1.8 MPa was measured according to the method described in ISO standard 75-1.
  • Thermal conductivity ⁇ was calculated by the following equation as a product of the thermal diffusivity ⁇ , the density ⁇ , and the specific heat Cp obtained by the following method.
  • ⁇ ⁇ ⁇ ⁇ ⁇ Cp ⁇ : thermal conductivity (W / (m ⁇ K)) ⁇ : Thermal diffusivity (m 2 / sec) ⁇ : Density (g / m 3 )
  • Cp Specific heat (J / g ⁇ K)
  • the thermal diffusivity ⁇ was measured with a laser flash method thermal constant measuring device TC-7000 (manufactured by ULVAC-RIKO) in the resin flow direction and thickness direction of the test piece prepared in (6) above.
  • the density ⁇ was measured using an electronic hydrometer ED-120T (manufactured by Mirage Trading Co.).
  • the specific heat Cp was measured using a differential scanning calorimeter DSC-7 (manufactured by Perkin Elmer) under the condition of a temperature rising rate of 10 ° C./min.
  • Polyamide resin (A1) PA 6: Polyamide 6 obtained by polymerization of ⁇ -caprolactam (relative viscosity 1.9, density 1.13 g / cm 3 )
  • PA66 polyamide 66 obtained by polymerization of hexamethylenediamine and adipic acid (relative viscosity 2.8, density 1.14 g / cm 3 )
  • Aliphatic polyester resin (A2) PLA1: Polylactic acid (manufactured by Nature Works, PLA6251D, melting point 165 ° C., density 1.24 g / cm 3 )
  • PLA2 Polylactic acid (Unitika Ltd., Terramac TE-7003, melting point 165 ° C., density 1.25 g / cm 3 )
  • GF Glass fiber (Owens Corning, average fiber diameter 10 ⁇ m, average fiber length 3 mm, density 2.50 g / cm 3 )
  • TC scale-like talc (manufactured by Nippon Talc Co., Ltd., average particle size 23 ⁇ m, thermal conductivity 5 to 10 W / (m ⁇ K), density 2.70 g / cm 3 )
  • MgO spherical magnesium oxide (manufactured by Tateho Chemical Co., Ltd., average particle size 30 ⁇ m, thermal conductivity 50 W / (m ⁇ K), density 3.58 g / cm 3 )
  • BN Hexagonal scaly boron nitride (manufactured by Electrochemical Co., Ltd., average particle size 15 ⁇ m, thermal conductivity 210 W / (m ⁇ K), density 2.26 g / cm 3 )
  • AL spherical aluminum oxide (manufactured by Micron,
  • Plasticizer / HB p-hydroxybenzoic acid alkyl ester (Kao Corporation, Exepearl HD-PB, liquid)
  • ADF Low molecular weight styrene-acrylic oligomer (BASF Corporation, JONCRYL ADF-1300, solid)
  • Additives FR Brominated flame retardant (IC-2, manufactured by ICL-IP)
  • Example 1 In a main hopper of a twin screw extruder (TEM 26SS manufactured by Toshiba Machine Co., Ltd., screw diameter 26 mm), 22 parts by mass of polyamide 6 (PA6), 78 parts by mass of flaky talc (TC), and 2 parts by mass of rosin (C1) The mixture was melted and kneaded at 260 ° C., extruded into a strand, cooled and solidified, and then cut into a pellet to obtain a resin composition. Next, this resin composition was injection molded at a cylinder temperature of 280 ° C. and a mold temperature of 100 ° C.
  • PA6 polyamide 6
  • TC flaky talc
  • C1 rosin
  • Examples 2 to 82, Comparative Examples 1 to 43 A resin composition and a molded body were obtained in the same manner as in Example 1 except that the resin composition and molding conditions were changed as shown in Tables 1 to 6. In addition, when using glass fiber as a filler, glass fiber was supplied from the middle by the side feeder. The evaluation results of the obtained molded products are shown in Tables 1 to 6.
  • the resin composition of the present invention has a long bar flow flow length, a low melt viscosity, excellent molding processability, and the obtained molded product has excellent mechanical properties. While maintaining the characteristics (bending strength and flexural modulus), the bleed-out property was good, and the produced housing-shaped molded body was excellent in heat dissipation.
  • the volume ratio (A / B) of the thermoplastic resin (A) to the filler (B) is 35/65 or less, and the filler relative to the thermoplastic resin (A).
  • the capacity ratio of (B) is high, a resin composition excellent in molding processability was obtained by using rosin (C) having a high acid value.
  • Examples 27 and 33 and Examples 66 and 69 are compared, Examples 33 and 66 using the filler (B) having a large average particle diameter are more preferable than Examples 27 and 69, respectively.
  • a resin composition having more excellent moldability was obtained.
  • an appropriate amount of a thermally conductive filler was used as the filler, so that the thermal conductivity was 0.5 W / (m ⁇ K) or higher and the thermal conductivity was high.
  • a shaped body was obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine thermoplastique contenant une résine thermoplastique (A), une charge (B) et une colophane (C), qui est caractérisée en ce que : la résine thermoplastique (A) est une résine de polyamide (A1), une résine de polyester aliphatique (A2) ou une résine de polyester semi-aromatique (A3) ; la colophane (C) est contenue dans une quantité de 0,3-5 parties en masse pour 100 parties en masse du total de la résine thermoplastique (A) et de la charge (B) ; et la colophane (C) a un indice d'acide de 60 mgKOH/g ou plus.
PCT/JP2012/072680 2011-11-10 2012-09-06 Composition de résine thermoplastique et corps moulé formé à partir de celle-ci Ceased WO2013069365A1 (fr)

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WO2015098508A1 (fr) * 2013-12-26 2015-07-02 ユニチカ株式会社 Composition de résine de polyamide retardatrice de flamme et article moulé la comprenant
JP2016006146A (ja) * 2014-05-26 2016-01-14 ユニチカ株式会社 熱伝導性樹脂組成物およびそれからなる成形体
JPWO2016093119A1 (ja) * 2014-12-09 2017-09-07 信越化学工業株式会社 車載ヘッドライト用ｌｅｄ光源
JP2017190407A (ja) * 2016-04-14 2017-10-19 ユニチカ株式会社 ポリアミド樹脂組成物およびそれからなる成形体
WO2018065055A1 (fr) * 2016-10-06 2018-04-12 Struers ApS Support de montage thermoplastique et son procédé de fabrication
WO2018074273A1 (fr) 2016-10-17 2018-04-26 荒川化学工業株式会社 Article moulé en plastique composite
JP2020523468A (ja) * 2017-06-14 2020-08-06 プレミックス・オサケユフティオＰｒｅｍｉｘ Ｏｙ 抗菌ポリマー組成物
WO2020189502A1 (fr) * 2019-03-20 2020-09-24 東洋紡株式会社 Composition de résine polyamide
US12098278B2 (en) 2019-03-20 2024-09-24 Toyobo Mc Corporation Polyamide resin composition
WO2025026811A1 (fr) * 2023-07-28 2025-02-06 Basf Se Composition polymère comprenant des fibres de verre recyclées
EP4414415A4 (fr) * 2021-10-07 2025-09-03 Toray Industries Composition de résine thermoplastique renforcée par des fibres
EP4303266A4 (fr) * 2021-03-02 2025-10-15 Dainippon Ink & Chemicals Composition de résine biodégradable et produit moulé associé

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WO2019079241A1 (fr) * 2017-10-18 2019-04-25 Ascend Performance Materials Operations Llc Compositions polyamides retardatrices de flamme, halogénées
CN112358687B (zh) * 2020-11-10 2023-06-20 江苏金发科技新材料有限公司 一种阻燃聚丙烯组合物及其制备方法
KR102311536B1 (ko) * 2021-04-22 2021-10-13 주식회사 성원 폐분체도료를 활용한 재생펠렛의 제조방법 및 이를 이용하여 제조한 폐분체도료를 활용한 재생펠렛
CN114316465A (zh) * 2021-12-13 2022-04-12 李庆安 一种基于电缆光缆包覆用强热塑性复合材料及其制作方法

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JPWO2015098508A1 (ja) * 2013-12-26 2017-03-23 ユニチカ株式会社 難燃性ポリアミド樹脂組成物およびそれからなる成形体
WO2015098508A1 (fr) * 2013-12-26 2015-07-02 ユニチカ株式会社 Composition de résine de polyamide retardatrice de flamme et article moulé la comprenant
JP2016006146A (ja) * 2014-05-26 2016-01-14 ユニチカ株式会社 熱伝導性樹脂組成物およびそれからなる成形体
JPWO2016093119A1 (ja) * 2014-12-09 2017-09-07 信越化学工業株式会社 車載ヘッドライト用ｌｅｄ光源
JP2017190407A (ja) * 2016-04-14 2017-10-19 ユニチカ株式会社 ポリアミド樹脂組成物およびそれからなる成形体
WO2018065055A1 (fr) * 2016-10-06 2018-04-12 Struers ApS Support de montage thermoplastique et son procédé de fabrication
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WO2018074273A1 (fr) 2016-10-17 2018-04-26 荒川化学工業株式会社 Article moulé en plastique composite
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WO2020189502A1 (fr) * 2019-03-20 2020-09-24 東洋紡株式会社 Composition de résine polyamide
US12071512B2 (en) 2019-03-20 2024-08-27 Toyobo Mc Corporation Polyamide resin composition
US12098278B2 (en) 2019-03-20 2024-09-24 Toyobo Mc Corporation Polyamide resin composition
JPWO2020189502A1 (fr) * 2019-03-20 2020-09-24
EP4303266A4 (fr) * 2021-03-02 2025-10-15 Dainippon Ink & Chemicals Composition de résine biodégradable et produit moulé associé
EP4414415A4 (fr) * 2021-10-07 2025-09-03 Toray Industries Composition de résine thermoplastique renforcée par des fibres
WO2025026811A1 (fr) * 2023-07-28 2025-02-06 Basf Se Composition polymère comprenant des fibres de verre recyclées

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CN103814082A (zh) 2014-05-21
JPWO2013069365A1 (ja) 2015-04-02

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